Resinous condensation products and method of producing same



Patented Feb. 13, 1940' v UNITED STATES PATENT crates RESINOUS CONDENSATION PRODUCTS AND METHOD OF PRODUCING SAW Israel Itosenblum, Jackson Heights, N. H.

newed March 2, 1933 1 Elaim. (CE. 260-=2tl) My invention relates to synthetic resins and has for its object to produce resinouscondens'ation products of great complexity and extraordinerily high molecular weight with the aid of a polyhydric inorganic acid or its anhydride.

It is also an object of the present inventionto produce synthetic resins of ready solubility in the common solvents, such as mineral spirits, toluoi, ethyl acetate, etc., and of substantially neutral reaction, good consistency and body, which are compatible with nitrocellulose and other cellulosic lacquers and may be used in conjunction therewith, and also with a great variety of natoral and synthetic gums used in the lacquer and varnish industry.

It is well known that polyhydric alcohols, such as glycerol, may be either completely or partially esterified with monobasic or polybasic acids to produce ester's which, in certain cases, are of resinous character or can be condensed or polymerized into resinous or approximately resinous substances by more or less prolonged heating at elevated temperatures. The reactions occurring during the formation ofrmany of the synthetic resinous products are not thoroughly understood,

but itis probable that during the first stages of the reaction a part of the polyhydrlc alcohol is under certain conditions only partially esterified (especially when an excess of the alcohol is present) and that during the subsequent heat- 0 ing the free hydroxyl groups of two molecules condense and become united through an oxygen bond to forms, more complex molecule. Accordingto the present invention, a plurality of molecules of partially esterifled polyhydric alcohols (which may or may not themselves be of resinous character) are united or condensed with the aid of an inorganic polybaslc acid or its anhydride which directly forms the bond between such molecules. In this way. 'a plurality of large 0 organic molecules may be condensed by an inorganic acid ofrelatively low molecular weight, so that a very complex product may be obtained with the use of a comparatively small quantity of inorganic acid. Preferably, the relative quantlties of'reacting materials'and the other conditions are so stances so produced contain one or more tree hydroxyl groups which may then be caused to condense, or the hydroxylated complexes may be treated with other substances, such as acids and acidic resins, as will be described more fully hereinbelow. In order that my invention may be better understood, I describe the same in connecregulated that the complex subtion with. the production of complex resins from magic acid or its anhydride, glycerol and boric ac Malic acid may be caused to be combined in any known manner with an excess of glycerclto produce hydroxy-esters, of which the followin simple compounds are illustrative:

Other compounds are doubtless produced but only these are represented for the sake of simplicity as they are sufilcient to illustrate the nature of the present invention. The mixture of hydroxy-esters is then caused to react with in c: -o-car-onon-n,o

United States Patents Products of greater solubility and flexibility may, in accordance with the present invention, be obtained by treating the boronized hydroiwesters with acids until the same are substan tainable from drying and non-drying oils and from fats. In general, I prefer to employ rosin or other natural resin (which is, of course, acidic in nature) in conjunction with any of the acids just specified. Improved resultsare generally obtained if the natural resin, if used, and particularly rosin, is first cracked or dry-distilled, as by heating to a temperature of about 260 C. or above. I may also employ, either alone or together with linoleic or any of the other acids mentioned, a condensation product of phenol, formaldehyde, a natural resin, such as rosin, and an organic salt, such as a zinc soap, specifically zinc abietate, as described in my Nos. 1,808,716 and 1,809,570, dated June 2 and June 9, 1931, respectively. The acidic compounds just enumerated will combine with the boronized hydroxy-esters of glycerol and malic acid and neutralize the same, thereby producing extremely complex esters of glycerol with malic acid, boric acid, and one or moreof the other organic acids mentioned above.

The reaction may be made to occur in steps, as by first treating the malic acid with glycerol and then reacting the hydroxy-esters so produced with boric acid and finally heating the boronized hydroxy-esters with one or more. of the other acids above mentioned until a substantially neutral product is obtained; or else all of the ingre dients in proper proportions may be made to react simultaneously. 7

Instead of combining the condensate of boric acid and the hydroxy glycerol-malic acid esters with the acids mentioned hereinabove, the free basic hydroxyls of these boronized esters may be combined with the acidic compounds obtained by condensing with an excess of boric acid the hydroxy-esters obtained by partially neutralizing glycerol with an organic acid, such as one or more of the acids mentioned above, but preferably with a high molecular weight fatty acid, such as linoleic acid. In this way complex compounds are obtained in which what may be regarded as a nucleus composed of an ester of-glycerol and malic acid is joined through boron bonds to one or more other glycerol-malic acid esters and to one or more glycerol esters of other acids. It will thus be clear that, by the aid of an inorganic polybasic condensing medium, I may obtain extremely complex resin molecules of very great variety.

In place of the condensate of boric acid with the hydroxy-esters obtained by partially neutralizing glycerol with a high molecular weight fatty acid, I may employ a condensate of boric acid with the hydroxy-esters obtained by partially neutralizing glycerol .with two organic acids, such as linoleic acid and the acid contained in rosin, or, asone of such acids, or alone, I may use the acidic condensate produced by condensing phenol, formaldehyde, rosin (or other natural resin) with an organic salt of zinc or other metal, such as calcium, strontium, barium, magnesium, lead,

3 hyde condensate.

etc. In general, I prefer to use, in place of the rosin as it is commercially available, rosin which has been heated or cracked in the presence of an organic zinc (or other metal) salt-phehol-alde- By the 'use of such zincphenol-aldehyde condensate, the product is made more resistant, while at the same time the formation of compounds which crystallize out from ethyl acetate solution and are not colloidal or film-forming is prevented. It will be understood that, in place of rosin, other natural resins, such as the fossil resins, may be employed which are similarly dry-distilled or cracked in the presence of an organic salt phenol-formaldehyde condensate.-

By' the above procedure, extremely complex resins are obtained which are highly weather and waterproof, have excellent body and are compatible with cellulosic lacquers. boronized condensate produce varnishes having a very glossy and lustrous surface. They also make excellent wood fillers and, as stated, may be used in conjunction with nitrocellulose lacquers.

In place of malic acid, I may use substantially equivalent quantities of maleic acid, or of the anhydrides of these acids, or mixtures thereof.

Several modes of carrying out my invention are described hereinbelow, but it will be understood that the examples are given by way of illustration only and are not to be construed in a limiting sense.

Example '1.134 grams of malic acid, 62 grams of boric acid and 200 grams of glycerol are heated at about 200 C. for three hours. There are then added 280 grams of linoleic acid and the heating continued, the temperature being gradually raised to about 240 C. The reaction is complete when a sample of the product is completely soluble in toluol. is compatible with nitrocellulose in all proportions and imparts to the lacquer great durability and gloss.

Example 2.-134 grams of malic acid, 10 grams The gum so produced My novel of boric acid, and 100 grams of glycerol are heated to about 200 C. and maintained at that temperature for two hours. There are then added 140 heating continued, the temperature being raised to about 230 to 240 C. The reaction is complete when a sample dissolves completely in toluol.

as zinc, as described in my above-mentioned patents, and 140 grams of stearic acid. The temperatureis maintained at about 240 C. until a sample is found to be completely soluble in toluol; The resin obtained is compatible with solutions of nitrocellulose.

' Example 4,-A mixture of 134 grams of malic acid, 31 grams of boric acid, 150 grams of glycerol, and 280 grams of linoleic acid are heated at about 180 C. until a sample taken from the reacting mass is found to be clear. The tem-- perature is then increased to about 230 C. and

the reacting mass kept'at such temperature until a sample is foundto begcompletely soluble in toluol.

Example 5.-280 grams of linoleic acid, 200 grams of glycerol, and 62 grams of boric acid are heated to about 150 C. for two hours. There grams of stearicacid or linoleic acid and the w are then added 134 grams of malic acid and the 7 5 acting mass is found to be soluble in toluol.

Example 6.-The procedure given under Example 5 may be followed except that, in place of the linolelc acid, there is used a mixture of linoleic and stearic acids in the equivalent mo-. lecular quantities.

Example 7.280 grams of linoleic acid, 200 grams of glycerol (98% pure), and 31 grams of boric acid are heated at about 180 C. for two hours. Thereare then added 67 grams of malic acid, and 300 grams of an organic zinc saltphenol-formaldehyde condensate (prepared as described in my above-mentioned patents) The temperature is permitted to rise about 230 C. and the mass kept at that temperature until a sample of the product forms a clear solution in toluol.

Example 8.--The procedure outlined under Example '7 is followed except that, in place of the zinc salt-phenol- -formaldehyde condensate, there is used an equivalent quantity of dry-distilled or non-distilled rosin or any dry-distilled fossil gum.

If desired, an excess of fatty acids may be employed in the examples given above because the same are compatible with mynovel boronized condensates.

By the above procedures, water-resistant-resins are obtained from dibasic aliphatic acids which are themselves quite soluble in water; and homogeneous, soluble resins are obtained in spite of the fact that glycerol, dibasic aliphatic acids like malic, maleic, succinic, tartaric etc., and relatively large quantities of fatty oil acids usually yield a permanently non-homogeneous system on reaction- As indicated above, any suitable polyhydric alcohol other than glycerol may be used, such as glycol, mannitol, etc.; in place of malic acid any other organic acid, or its anhydride, monobasic or polybasic, may be used, such as succinic, tar- 5 taric, maleic, etc., or any of the high molecular weight acids mentioned above; and in place of boric acid any other suitable polyhydric inorganic acid, such as telluric, phosphoric, arsenic acids, etc., or their anhydrldes, may be employed. 10'

If desired, the reactions described hereinabove may be made to take place in the presence of a natural resin, preferably dry-distilled, which may act as a solvent, or may supply one of the reacting acids.

The present application is a division of my co-pending application, Serial No. 438,901, filed March 25, 1930.

Where in the claim I employ the term malicmaleic group" the same is to be understood to 20 mean malic acid, m'aleic acid, malo-malic acid, their anhydrides, or mixtures of these acidic substances; while the term'boric acid includes also boric anhydride.

Variations may be resorted to within the-scope 25 of the appended claim without departing from the spirit of the invention.

What is claimed is: i v

The method of producing a resinous condensation product suitable for the manufacture of a0 water-resisting coating compositions which com-, prises reacting a polyhydric alcohol'with a fatty oil acid, boric acid and maleic acid, and simultaneousiy or subsequently heating the mass with a a rosin-containing condensate of a phenol and as formaldehyde. v m ROBINBLUI. 

